CHEMISTRY

Crash Course for

JEE Main 2020

THERMODYNAMICS

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 THERMODYNAMICS
EXERCISE - 1
1. The heat of reaction at constant volume (E) and that at constant pressure (H) are related as-
(A) E = H + nRT (B) H = E –nRT
(C) H = E+ nRT (D) H =  E + nRT
2. For a chemical reaction,
2A2 (g) + 5B2 (g)  2A2B5 (g),
at 27ºC the difference between H and  E is X. Then the ratio X/R -
(A) Zero (B) Unity(C) (C) – 5 ×100 (D)–1.5 × 103
3. X g of ethanal (CH3CHO) was subjected to combusion in a bomb calorimeter and the heat
produced is Y joules. Then which of following is correct -
44Y
J mol –1

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(A) E (comb.) = – Y kJ (B) E (comb.) = –
X
44Y
(C) H (comb.) = – J mol –1 (D) H (comb.) = – Y J mol –1
X
4. Latent heat of vaporisation of a liquid at 500 K and 1 atm pressure is 10.00 kcal/mol. What will be

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the change in internal energy (E of 3 mol of liquid at same temperature)-
(A) 13.0 kcal (B) – 13.0 kcal (C) 27.0 kcal (D) – 27.0 kcal
5. Ammonium nitrate can decompose with explosion by the following reaction.
NH4NO3 (s)  N2O (g) + 2H2O
H = –37.0 KJ/mol N
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Calculate the heat produced when 2.50g of NH4NO3 decomposes -
(A) 1.06 KJ (B) 0.96KJ (C) 1.16 KJ (D) 1.26 KJ
6. Difference between H and E for the combusion of liquid benzene at 27°C is -
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(A) 7.48 kJ (B) 3.74 kJ (C) 14.86 kJ (D) 5.73 kJ
–3 3 –2 3
7. An ideal gas expands in volume from 1 × 10 m to 1 × 10 m at 300 K against a constant pressure
of 1 × 105 Nm–2 . The work is :
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(A) – 900 J (B) – 900 kJ (C) 270 kJ (D) + 900 kJ

8. For the reaction between CO2 and graphite
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CO2 (g) + C(s) 2CO(g)

H = + 170.0 kJ and S= 170 JK-1. The reaction is spontaneous at -
(A) 298 K (B) 500 K (C) 900 K (D) 1200 K.
9. For the spontaniety of a reaction , which is true-
(A) G = +ve, H = + ve (B) H = +ve, S = - ve
(C) G = + ve, H = - ve (D) H = - ve, S = + ve
10. For an endothermic reaction S is positive. The reaction is -
(A) Feasible at all temperatures (B) Feasible when TS > H
(C) Feasible when H >TS (D) Not feasible at all
11. The molar heat capacity of a monoatomic gas for which the ratio of pressure and volume is one.
(A) 4/2 R (B) 3/2 R (C) 5/2 R (D) zero
12. The work done in an open vessel when 112 gm of Fe reacts with dil. HCl to form FeCl2 at 27°C will
be
(A) 1200 cal (B) 600 cal (C) 300 cal (D) 200 cal

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 THERMODYNAMICS
13. 16 gm of O2 expand at STP to occupy double its original volume. The work done during the process
will be
(A) 260 cal (B) 180 cal (C) 130 cal (D) 271.49 cal
14. One mole of ideal gas is allowed to expand reversibly and adiabatically from a temperature of 27°C.
If the work done during the process is 3 kJ. The final temperature will be equal to
(Cv = 20 J K–1)
(A) 150 K (B) 100 K (C) 26.85 K (D) 295 K
15. Consider the reaction, N2 (g) + 3H2 (g)  2NH3 (g); carried out at constant temperature and
pressure. If H and U are enthalpy change and internal energy change respectively, which of the
following expressions is true ?
(A) H = 0 (B) H = U (C) H < U (D) H > U
16. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If Ti is the

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initial temperature and Tf is the final temperature, which of the following statements is correct ?
(A) Tf > Ti for reversible process but Tf = Ti for irreversible process
(B) (Tf)rev = (Tf)irrev
(C) Tf = Ti for both reversible and irreversible processes

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(D) (Tf)irrev > (Tf)rev
17. (HU) for the formation of carbon monoxide (CO) from its elements at 298 K is
(R = 8.314 J K1 mol1)

18.
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(A) 1238.78 J mol1 (B) 2477.57 J mol1 (C) 2477.57 J mol1 (D) 1238.78 J mol1
Identify the correct statement regarding a spontaneous process :
(A) Exothermic processes are always spontaneous.
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(B) Lowering of energy in the reaction process is the only criterion for spontaneity.
(C) For a spontaneous process in an isolated system, the change in entropy is positive.
(D) Endothermic processes are never spotaneous.
19. In conversion of lime-stone to lime, CaCO3 (s) CaO(s) + CO2 (g) the values of H0 and S0 are
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+ 179.1 kJ mol–1 and 160.2 J/K respectively at 298 K and 1 bar. Assuming that H° and S° do not
change with temperature, temperature above which conversion of limestone to lime will be spontaneous
is :
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(A) 845 K (B) 1118 K (C) 1008 (D) 1200 K

20. Determine which of the following reactions at constant pressure represent surrounding that do work on
the system
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I. 4NH3 (g) + 7O2 (g)  4NO2 (g) + 6H2O (g)

II. CO (g) + 2H2 (g)  CH3OH (  )
III. C (s, graphite) + H2O (g)  CO (g) + H2 (g)
IV. H2O (s)  H2O (
(A) III, IV (B) II and III (C) II, IV (D) I and II, IV
21. An ideal gas is taken around the cycle ABCA as shown in P-V diagram. The net work done by the gas
during the cycle is equal to :

(A) 12P1V1 (B) 6P1V1 (C) 5P1V1 (D) P1V1

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 THERMODYNAMICS
22. 1 mole of NH3 gas at 27° C is expanded in reversible adiabatic condition to make volume 8 times (
= 1.33). Final temperature and work done respectively are :
(A) 150 K, 900 cal (B) 150 K, 400 cal (C) 250 K, 1000 cal (D) 200 K, 800 cal
23. A certain mass of gas is expanded from (1L, 10 atm) to (4L, 5 atm) against a constant external
pressure of 1 atm. If initial temperature of gas is 300 K and the heat capacity of process is 50 J/°C.
Then the enthalpy change during the process is (1L atm ~ 100 J)
(A) H = 15 kJ (B) H = 15.7 kJ (C) H = 14.4 kJ (D) H = 14.7 kJ
24. The entropy change when two moles of ideal monoatomic gas is heated from 200 to 300ºC reversibly
and isochorically ?
3  300  5  573   573  3  573 
(A) 2
R ln  200  (B) 2
R ln  273  (C) 3R ln  473  (D) 2
R ln  473 
25. 1 mole of an ideal gas at 25°C is subjected to expand reversibly and adiabatically to ten times of its

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initial volume. Calculate the change in entropy during expansion (in J k–1 mol–1)
(A) 19.15 (B) – 19.15 (C) 4.7 (D) zero
26. What is the change in entropy when 2.5 mole of water is heated from 27ºC to 87ºC ? Assume that the
heat capacity is constant. (Cp,m (H2O) = 4.2 J/g-K ln (1.2) = 0.18)
(A) 16.6 J/K (B) 9 J/K (C) 34.02 J/K (D) 1.89 J/K

D
27. Two mole of an ideal gas is expanded irreversibly and isothermally at 37ºC until its volume is doubled
and 3.41 kJ heat is absorbed from surrounding. Stotal (system + surrounding) is :
(A) –0.52 J/K (B) 0.52 J/K (C) 22.52 J/K (D) 0
28. Given rSº = –266 and the listed [Sºm values]
calculate Sº for Fe3O4 (s) : N
SI
4Fe3O4 (s) [..............] + O2 (g) [205]  6Fe2O3 (s) [87]
(A) +111.1 (B) +122.4 (C) 145.75 (D) 248.25
29. In the cyclic process shown in P-V diagram, the magnitude of the work done is :
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O
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2 2
P P   V  V1  
(A)  2 1 (B)  2  (C) (P2 – P1) (V2 – V1) (D)  (V2 – V1)2
 2   2  4

30. Work for the following process ABCD on a monoatomic gas is :

P
P0 A B

Isothermal

C
D

V0 2V0 4V0 V
(A) w = – 2 P0 V0 ln 2, (B) w = – 2 P0 V0 ln 2,
(C) w = – P0 V0 (1+ ln 2), (D) w = – P0 V0 ln 2,

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 THERMODYNAMICS
31. C2H6 (g) + 3.5 O2 (g)  2CO2 (g) + 3H2O (g)
Svap (H2O,l) = x1 cal K-1 (boiling point = T1)
Hf (H2O,l ) = x2
Hf (CO2) = x3
Hf (C2H6) = x4
Hence, H for the reaction is -
(A) 2x3 + 3x2 – x4 (B) 2x3 + 3x2 – x4 + 3x1T1
(C) 2x3 + 3x2 – x4 – 3x1T1 (D) x1T1 + X2 + X3 – x4
32. Consider the Gºƒ and Hºƒ (kJ/mol) for the following oxides. Which oxide can be most easily
decomposed to form the metal and oxygen gas ?
(A) ZnO (Gº = –318.4, Hº = –348.3) (B) Cu2O (Gº = –146.0, Hº = –168.8)
(C) HgO (Gº = –58.5, Hº = –90.8) (D) PbO (Gº = –187.9, Hº = –217.3)

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33. One mole of an ideal diatomic gas (Cv = 5 cal) was transformed from initial 25°C and 1 L to the state
when temperature is 100°C and volume 10 L. The entropy change of the process can be expressed as
(R = 2 calories/mol/K)
298 373

D
(A) 3 ln 373
+ 2 ln 10 (B) 5 ln 298
+ 2 ln 10

373 1 373 1
(C) 7 ln + 2 ln (D) 5 ln + 2 ln
34.
298 10

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K and 0.92 J/K mol at 20 K, then molar entropy at 20 K is :
298 10
For a perfectly crystalline solid Cp,m = aT3 + bT, where a and b constant. If Cp,m is 0.40 J/K mol at 10
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(A) 0.92 J/K mol (B) 8.66 J/K mol (C) 0.813 J/K mol (D) None of these
35. Latent heat of vaporisation of water is 540 cal g–1. The entropy change during the evaporation of 1
mole of water at 100ºC is -
(A) 5.4 cal K–1 mol–1 (B) 20 cal K–1 mol–1
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–1 –1
(C) 25 cal K mol (D) 26.06 cal K–1 mol–1
36. The solubility product of AgCl is 1.6 × 10–10 and log ksp is –9.80. The value of Gº for the
process,
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AgCl (s) + aq Ag+ (aq) + Cl– (aq) is -

(A) – 55.9 kJ (B) + 55.9 kJ (C) +100.8 kJ (D) – 100.8 kJ
37. Which of the following process involves decrease in the entropy of system -
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(A) Br2()  Br2(g) (B) Elongating the rubber band

(C) N2(g) [1 atm]  N2(g) [10 atm] (D) Hard boiling of egg
38. The standard free energy change Gº is related to equilibrium constant, Kp as -
G 
 e 
(A) Kp = –RT n Gº (B) Kp =  RT 
 

G
(C) Kp = – (D) Kp = e(–Gº/RT)
RT
39. In an irreversible process taking place at constant T and P and in which only pressure-volume work is
being done the change in Gibbs free energy (dG) and change in entropy (dS) satisfy the criteria -
(A) (dS)V, E = 0, (dG)T, P = 0 (B) (dS)V, E = 0, (dG)T, P > 0
(C) (dS)V, E < 0, (dG)T, P < 0 (D) (dS)V, E > 0, (dG)T, P < 0

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 THERMODYNAMICS
40. When two equal sized pieces of the same metal at different temperatures Th (hot piece) and Tc(cold
piece) are brought into contact into thermal contact and isolated from it's surrounding. The total change
in entropy of system is given by
Tc  Th T2 (Tc  Th ) 2 (Tc  Th ) 2
(A) Cvln (B) Cvln (C) Cvln (D) Cvln
2Tc T1 2Th .Tc 4Th .Tc
41. What can be concluded about the values of H and S from this graph?

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(A) H > 0, S > 0 (B) H > 0, S < 0 (C) H < 0, S > 0 (D) H < 0, S < 0
42. Which of the following statement(s) is/are incorrect:
Statement (a) : Reversible isothermal compression of an ideal gas represents the limiting minimum

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value of the workdone (|w|) by the surrounding on the system.
Statement (b): In an irreversible process, the cyclic integral of work is not zero.
 Cp , m 

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Statement (c): For thermodynamic changes in adiabatic process T

 R 



.P = constant
Statement (d) : Ssystem is zero for reversible adiabatic expansion of an ideal gas.
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(A) Statement c (B) Statement a, b, c (C) Statement a, b, d (D) All
43. 9.0 gm ice at 0°C is mixed with 36 gm of water at 50°C in a thermally insulated container.
Using the following data, answer the question that follow
CP (H2O) = 4.18 Jg–1K–1 ; Hfusion (ice) = 335 J g–1
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Sice is
(A) 11.04 JK–1 (B) 3.16 JK–1 (C) 14.2 JK–1 (D) 7.84 JK–1
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44. Consider the reaction, N2 (g) + 3H2 (g)  2NH3 (g); carried out at constant temperature and
pressure. If H and U are enthalpy change and internal energy change respectively, which of the
following expressions is true ?
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(A) H = 0 (B) H = U (C) H < U (D) H > U

45. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If Ti is the
initial temperature and Tf is the final temperature, which of the following statements is correct ?
(A) Tf > Ti for reversible process but Tf = Ti for irreversible process
(B) (Tf)rev = (Tf)irrev
(C) Tf = Ti for both reversible and irreversible processes
(D) (Tf)irrev > (Tf)rev
46. (HU) for the formation of carbon monoxide (CO) from its elements at 298 K is
(R = 8.314 J K1 mol1)
(A) 1238.78 J mol1 (B) 2477.57 J mol1 (C) 2477.57 J mol1 (D) 1238.78 J mol1
47. Identify the correct statement regarding a spontaneous process :
(A) Exothermic processes are always spontaneous.
(B) Lowering of energy in the reaction process is the only criterion for spontaneity.
(C) For a spontaneous process in an isolated system, the change in entropy is positive.
(D) Endothermic processes are never spotaneous.
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 THERMODYNAMICS

48. In conversion of lime-stone to lime, CaCO3 (s) CaO(s) + CO2 (g) the values of H0 and S0 are
+ 179.1 kJ mol–1 and 160.2 J/K respectively at 298 K and 1 bar. Assuming that H° and S° do not
change with temperature, temperature above which conversion of limestone to lime will be spontaneous
is :
(A) 845 K (B) 1118 K (C) 1008 (D) 1200 K
49. -1 -1 -1
At 1 atm pressure, Svap = 75 JK mol and Hvap = 30 KJ mol for a given reaction. The
normal boiling point of reaction is - [A]
(A) 400 K (B) 330 K (C) 200 K (D) 110 K
50. At 27ºC for reaction [B]
15
C6H6(l) + O2(g)  6CO2(g) + 3H2O(l)
2

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proceeds spontaneously because the magnitude of-
(A) H = TS (B) H > TS (C) H < TS (D) H > 0, TS < 0
51. For a reaction A + B  AB, Cp is given by the equation 40 + 5 × 10 T JK–1 in the temperature
–3

range 300 – 600K. The enthalpy of the reaction at 300 K is –25 KJ, the enthalpy of reaction at 450
K is -

D
(A) – 10.4 K J (B) – 18.72 KJ (C) –25.64 KJ (D) –38.93 KJ
52. The boiling point of a substance X at 1 atm pressure is 500 K. The enthalpy of vapourisation at the
boiling point of X(l) is 80 kJ/mol.

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The molar specific heat of X (l) = 5 × 10–3 kJ/mol and CP of X(g) = 5 × 10–4 kJ/mol.
What is the molar latent heat of vapourisation of X(l) at 800 K and at 1 atm ?
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(A) Lesser than 80 kJ
(B) Greater than 80 kJ
(C) Equal to 80 kJ
(D) Since 800 K is the higher temperature than the boiling point of X() ; therefore, enthalpy of
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vapourisation is not applicable


53. G F for the formation of HI (g) from its gaseous elements is –9.67 KJ/mol at 500K. When the partial
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pressure of HI is 10.0 atm and of I2 is 0.001 atm. What must be the partial pressure of hydrogen at this
temperature to reduce the magnitude of G for the reaction to zero -
(A) 103 atm (B) 103 atm (C) 855 atm (D) 10 atm
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54. Which of the following statement(s) is/are correct :

Statement (a) : If neither heat nor matter can enter or leave a system, that system must be isolated.
Statement (b) : q, w, E and H all are zero for adiabatic expansion of non ideal gas into vaccum
Statement (c) : G is a state function
Statement (d) : pH is an intensive property
(A) Statement a, b, d (B) Statement b, c, d (C) Statement b, d (D) Only b is correct
55. Which of the following statement(s) is/are correct:
Statement (a) : In any closed system with P, V work only, G is always minimized at equilibrium.
Statement (b) : G is always zero for a reversible process in a closed system.
Statement (c) : G° for an ideal gas reaction is a function of pressure.
Statement (d) : For an irreversible, isothermal, isobaric process in a closed system with P, V
work only. G must be negative.
(A) Statement a, b, d (B) Statement b, c, d (C) Statement c, d (D) Only statement d

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 THERMODYNAMICS
56. Which of the following statement(s) is/are correct :
Statement (a) : The entropy of isolated system with P–V work only is always maximized at equilibrium
Statement (b) : It is possible for the entropy of close system to decrease substantially in an irreversible
process.
Statement (c) : Entropy can be created but not destroyed.
Statement (d) :Ssystem is always zero for reversible process in an isolated system
(A) Statement a, b, c (B) Statement b,d (C) Statement a, b, d (D) All
57. An exothermic reaction is represented by the graph :

(A) (B) (C) (D)

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58. For a process which follows the equation PV3 = C, the work done when one mole of ideal gas was
taken from 1 atm to 2 2 atm starting from initial temperature of 300 K is
(A) 300 R (B) 150 R (C) 600 R (D) 900 R

D
59. The normal boiling point of a liquid 'A' is 350 K. Hvap at normal boiling point is 35 kJ/mole. Pick out
the correct statement(s). (Assume Hvap to be independent of pressure).
(A) Svaporisation > 100 J/Kmole at 350 K and 0.5 atm

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(B) Svaporisation < 100 J/K mole at 350 K and 0.5 atm
(C) Svaporisation < 100 J/K mole at 350 K and 2 atm
(D) Svaporisation = 100 J/K mole at 350 K and 2 atm
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60. A student found that 310 kJ of energy was released on burning 10 g of propan-1-ol,
CH3CH2CH2OH. From this experiment, what is the enthalpy of combustion, in kJmol–1, of propan-
1-ol?
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(A) –310 (B) –1296 (C) –1860 (D) –3100

Numerical Type Questions

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61. The enthalpy of vaporisation of liquid diethyl ether –(C2H5)2O, is 26.0 kJ mol–1 at its boiling point
(35.0ºC). Calculate S for conversion of vapour to liquid at 35ºC.
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62. The standard enthalpies of formation of the following substances in KJ/mole are
OF2 (g) = 20 ; H2O (g) = – 250 and HF (g) = – 270
Determine the standard decrease in internal energy at 300 K for the following reaction in nearest
possible integers in KJ/mol at 298 K.
OF2 (g) + H2O (g)  O2 (g) + 2 HF (g)
R = 8.3 JK–1 mol–1
63. An ideal gas is taken through the cycle A  B  C  A as shown in the figure. If net heat
supplied to the gas in the cycle is 5J, the work done on the gas in the process C A is ………J-
C B
2

V
in m3 1 A

10
P  in N/m2

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 THERMODYNAMICS
64. A gas absorbs 200 J of heat and expands against the external pressure of 1.5 atm from a volume of 0.5
litre. Calculate the change in internal energy.
Ans- +124.025 J
65. The equilibrium constant for the reaction given below is 2.0 × 10–7 at 300 K.
PCl5(g)  PCl3(g) + Cl2(g)
Also, calculate the standard entropy change if Hº = 28.40 kJ mol–1.
Sol.  Sº = –33.6 JK–1
66. One mole of a perfect monoatomic gas is put through a cycle consisting of the following three reversible
steps :
T1 T2
(20, 1) (20, 10)
A B

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P

C
T1 (2, 10)

D
V
Calculate the net work done by the system in the cycle
Ans- w = +3262.88 cal
67.

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Find out whether it is possible to reduce MgO using carbon at 298 K. If not, at what temperature it
becomes spontaneous. For reaction, MgO (s) + C(s)  Mg(s) + CO(g), rH = + 491.18 kJ
mol–1 and rS = 197.67 JK–1 mol–1.
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[Ans. At 298 K G° = + 432.274 KJ/mole, non spontaneous; T > 2484.8 K]
68. With what minimum pressure must a given volume of nitrogen, originally at 373 K and 1 atm, be
5
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adiabatically compressed in order to raise its temperature to 573 K. Given CV, m = R.
2
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[Ans. P2 = 2.876 atm]

69. Predict whether the entropy change of the system in each of the following process is positive or
negative.
ET

(a) CaCO3(s)  CaO(s) + CO2(g) (b) N2(g) + 3H2(g)  2NH3(g)

(c) N2(g) + O2(g)  2NO(g) (d) HCl(g) + NH3(g)  NH4Cl(s)
(e) 2SO2(g) + O2(g)  2SO3(g) (f) Cooling of N2(g) from 20°C to –50°C
Sol. (a) positive (b) negative
(c) small, the sign of S is impossible to predict (d) negative
(e) negative (f) negative
70. For the reaction : N2O4(g) 2NO2 (g)
(i) In a mixture of 5 mol NO2 and 5 mol N2O4 and pressure of 20 bar. Calculate the value of G for
the reaction. Given Gf° (NO2) = 50 kJ / mol, Gf° (N2O4) = 100 kJ / mol and T = 298 K.
[Given at T = 298 K, 2.303 RT = 5.7 kJ / mol.]
Ans - G = – 5700 J/mol

71. What is rG (KJ/mole) for synthesis of ammonia at 298 K at following sets of partial pressure:
N2(g) + 3H2(g) l 2NH3(g) ; rG° = –33 KJ/mole. [Take R = 8.3 J/K mole, log2 = 0.3; log3 = 0.48]

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 THERMODYNAMICS

Gas N2 H2 NH3

Pressure (atm) 1 3 0.02

72. For the hypothetical reaction
A2(g) + B2(g) l 2AB(g)
rG° and rS° are 20 kJ/mol & –20 JK–1 mol–1 respectively at 200 K.
If rCp is 20 JK–1 mol–1 then rH° at 400 K is
73. Calculate the maximum work done by the gas when pressure on 10 gm of H2 is reduced from 20 to 2
atm at constant temperature of 300 K. The gas behaves ideally.
74. S for freezing of 5 g of H2O (l) (Enthalpy of fusion is 80 cal/g) at 0°C and 1 atm is
75. The heat of vaporisation : Hvap, of CCl4
at 27°C is 42 kJ/mole

IA
CCl4(l)  CCl4(g) : Hvap = 42.0 kJ / mole
If 1 mole of liquid CCl4 at 27°C has entropy of 214 J/K mole, what is the entropy (in J/K-mol) of 1
mole of vapour in equilibrium with liquid at this temperature.

D
N
SI
O
O
ET

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 THERMODYNAMICS
EXERCISE - 2
PART - I
PREVIOUS YEAR QUESTIONS (AIEEE/JEE-MAIN)
1. An ideal gas expands in volume from 1 × 10–3 m3 to 1 × 10–2 m3 at 300 K against a constant pressure of
1 × 105 Nm–2 . The work is : [AIEEE 2004]
(A) – 900 J (B) – 900 kJ (C) 270 kJ (D) + 900 kJ
2. Consider the reaction, N2 (g) + 3H2 (g)  2NH3 (g); carried out at constant temperature and pressure. If H and
U are enthalpy change and internal energy change respectively, which of the following expressions is true ?
[AIEEE 2005]
(A) H = 0 (B) H = U (C) H < U (D) H > U
3. For a spontaneous reaction the G, equilibrium constant (K) and E°cell will be respectively [AIEEE 2005]
(A) – ve, > 1, + ve (B) + ve, > 1, – ve (C) – ve, < 1, –ve (D) – ve, > 1, – ve

IA
4. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If Ti is the initial tempera-
ture and Tf is the final temperature, which of the following statements is correct ? [AIEEE 2006]
(A) Tf > Ti for reversible process but Tf = Ti for irreversible process
(B) (Tf)rev = (Tf)irrev
(C) Tf = Ti for both reversible and irreversible processes

D
(D) (Tf)irrev > (Tf)rev
5. Assuming that water vapour is an ideal gas, the internal energy change (U) when 1 mol of water is vapourised at
1 bar pressure and 100°C, (Given : Molar enthalpy of vapourization of water at 1 bar and 373 K = 41 kJ mol–1 and

6.
R = 8.3 J mol–1 K–1) will be :
(A) 37.904 kJ mol–1 (B) 41.00 kJ mol–1
N (C) 4.100 kJ mol–1
Identify the correct statement regarding a spontaneous process :
(D) 3.7904 mol–1
[AIEEE 2007]

[AIEEE 2007]
SI
(A) Exothermic processes are always spontaneous.
(B) Lowering of energy in the reaction process is the only criterion for spontaneity.
(C) For a spontaneous process in an isolated system, the change in entropy is positive.
(D) Endothermic processes are never spontaneous.
O
7. In conversion of lime-stone to lime, CaCO3 (s) CaO(s) + CO2 (g) the values of H0 and S0 are + 179.1 kJ mol–1
and 160.2 J/K respectively at 298 K and 1 bar. Assuming that H° and S° do not change with temperature,
temperature above which conversion of limestone to lime will be spontaneous is : [AIEEE 2007]
O

(A) 845 K (B) 1118 K (C) 1008 (D) 1200 K

8. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1, respectively. [AIEEE 2008]
1 3
For the reaction, X + Y  XY3 H = – 30 kJ. To be at equilibrium the temperature will be :
ET

2 2 2 2
(A) 500 K (B) 750 K (C) 1000 K (D) 1250 K
9. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
3
CH3OH() + O (g) CO2(g) + 2H2O() [AIEEE 2009]
2 2
At 298 K, standard Gibb’s energies of formation for CH3OH(), H2O() and CO2 (g) are –166.2, –237.2 and
–394.4 kJ mol–1 respectively. If standard enthalpy of combustion of methanol is –726kJ mol–1, efficiency of the fuel
cell will be
(A) 87% (B) 90% (C) 97% (D) 80%
10. For a particular reversible reaction at temperature T, H and S were found to be both +ve. If Te is the temperature
at equilibrium, the reaction would be spontaneous when. [AIEEE 2010]
(A) Te > T (B) T > Te (C) Te is 5 times T (D) T = Te

11. The entropy change involved in the isothermal reversible expansion of 2 moles of an ideal gas from a volume of 10
dm3 to a volume of 100 dm3 at 27°C is : [AIEEE 2011]
(A) 38.3 J mol–1 K–1 (B) 35.8 J mol–1 K–1 (C) 32.3 J mol–1 K–1 (D) 42.3 J mol–1 K–1
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 THERMODYNAMICS
12. In view of the signs of rGº for the following reactions :
PbO2 + Pb  2PbO, rGº < 0
SnO2 + Sn  2SnO, rGº > 0,
which oxidation states are more characteristics for lead and tin ? [AIEEE 2011]
(A) For lead +2, for tin +2 (B) For lead +4, for tin +4
(C) For lead +2, for tin +4 (D) For lead +4, for tin +2
13. The incorrect expression among the following is : [AIEEE 2012]

G system Vf
(A) =–T (B) In isothermal process, wreversible = –nRT  n
S total Vi

Hº  TSº
(C) lnK = (D) K = e–Gº/RT
RT

IA
14. A piston filled with 0.04 mol of an ideal gas expands reversibly from 50.0 mL to 375 mL at a constant temperature of
37.0ºC. As it does so, it absorbs 208 J of heat. The values of q and w for the process will be:
(R = 8.314 J/mol K) (ln 7.5 = 2.01) [JEE 2013, (Mains)]
(A) q = +208 J, w = – 208 J (B) q = –208 J, w = – 208 J
(C) q = –208 J, w = + 208 J (D) q = +208 J, w = + 208 J

D
15. The heats of combustion of carbon and carbon monoxide are –393.5 and –283.5 kJ mol–1 respectively. The heat of
formation (in kJ) of carbon monoxide per mole is: [JEE 2016, (Mains)]
(A) 676.5 (B) –676.5 (C) –110.5 (D) 110.5
16. U is equal to :
(A) Isochoric work (B) Isobaric work N (C) Adiabatic work
[JEE 2017, (Mains)]
(D) Isothermal work
SI
17. Which of the following lines correctly show the temperature dependence of equilibrium constant, K, for an
exothermic reaction ? ln K [JEE 2018, (Mains)]
a
(A) b and c
O

(B) c and d b
1
(C) a and d (0,0) T(K)
O

××
(D) a and b ××
××
××
××
×× c
××
××
ET

××
××
d
18. The combustion of benzene (1) gives CO2(g) and H2O(l). Given that heat of combustion of benzene at constant
volume is –3263.9 kJ mol–1 at 25°C; heat of combustion (in kJ mol–1) of benzene at constant pressure will be :
(R = 8.314 JK–1 mol–1) [JEE MAIN 2018]
(A) –452.46 (B) 3260 (C) –3267.6 (D) 4152.6

19. A process will be spontaneous at all temperatures if :- [JEE MAIN (Online) 2019]
(A) H > 0 and S < 0 (B) H < 0 and S > 0 (C) H > 0 and S > 0 (D) H < 0 and S < 0

20. The difference between H and U (H–U), when the combustion of one mole of heptane (1) is carried out at a
temperature T, is equal to: [JEE MAIN (Online) 2019]
(A) 3RT (B) –3RT (C) –4RT (D) 4RT

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 THERMODYNAMICS
21. Two blocks of the same metal having same mass and at temperature T1 and T2, respectively. are brought in
contact with each other and allowed to attain thermal equilibrium at constant pressure. The change in entropy,
S, for this process is : [JEE MAIN (Online) 2019]

1
    T1  T2  2 
 T  T2    T1  T2  2
 T  T 
(A) 2CP ln  1  (B) 2CP ln (C) CP ln   (D) 2CP ln  1 2 
 4T1T2   T1T2   4T1T2   2T1T2 
 

22. The standard reaction Gibbs energy for a chemical reaction at an absolute temperature T is given by
r Gº = A – Bt [JEE MAIN (Online) 2019]
Where A and B are non-zero constants. Which of the following is TRUE about this reaction ?
(A) Exothermic if B < 0 (B) Exothermic if A > 0 and B < 0

IA
(C) Endothermic if A < 0 and B > 0 (D) Endothermic if A > 0

23. An ideal gas is allowed to expand from 1 L to 10 L against a constant external pressure of 1 bar. The work done in
kJ is : [JEE MAIN (Online) 2019]

D
(A) –9.0 (B) +10.0 (C) –0.9 (D) –2.0

24.

(A) 2.85 (B) 11.4

N
Enthalpy of sublimation of iodine is 24 cal g–1 at 200°C. If specific heat of I2(s) and I2(vap) are 0.055 and 0.031 cal
g–1 K–1 respectively, then enthalpy of sublimation of iodine at 250°C in cal g–1 is : [JEE MAIN (Online) 2019]
(C) 5.7 (D) 22.8
SI
25. The INCORRECT match in the following is : [JEE MAIN (Online) 2019]
(A) Gº < 0, K < 1 (B) Gº = 0, K = 1 (C) Gº > 0, K < 1 (D) Gº < 0, K > 1
O

26. Which one of the following equations does not correctly represent the first law of thermodynamics for the given
processes involving an ideal gas ? (Assume nonexpansion work is zero) [JEE MAIN (Online) 2019]
O

(A) Cyclic process : q = – w (B) Isothermal process : q = – w

(C) Adiabatic process : U = – w (D) Isochoric process : U = q
ET

27. For silver, Cp(JK–1 mol–1) = 23 + 0.01T. If the temperature (T) of 3 moles of silver is raised from 300K to 1000 K at 1
atm pressure, the value of H will be close to [JEE MAIN (Online) 2019]
(A) 21 kJ (B) 16 kJ (C) 13 kJ (D) 62 kJ

28. 5 moles of an ideal gas at 100 K are allowed to undergo reversible compression till its temperature becomes 200
K. If CV = 28 JK–1 mol–1, calculate U and pV for this process. (R = 8.0 JK–1 mol–1] [JEE MAIN (Online) 2019]
(A) U = 14 kJ; (pV) = 4 kJ (B) U = 14 kJ; (pV) = 18 kJ
(C) U = 2.8 kJ; (pV) = 0.8 kJ (D) U = 14 kJ; (pV) = 0.8 kJ

29. Among the following, the set of parameters that represents path function, is : [JEE MAIN (Online) 2019]
(1) q + w (2) q (3) w (4) H–TS
(A) (1) and (4) (B) (2), (3) and (4) (C) (2) and (3) (D) (1), (2) and (3)

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 THERMODYNAMICS
PREVIOUS YEAR QUESTIONS
PART -II (JEE ADVANCED)
1. 2 moles of ideal gas is expanded isothermally & reversibly from 1 litre to 10 litre. Find the enthalpy change
in kJ mol –1. [JEE 2004]
(A) 0 (B) 11.7 (C) – 11.7 (D) 25

2. There is 1 mol liquid (molar volume 100 ml) in an adiabatic container initial, pressure being 1 bar Now the pressure
is steeply increased to 100 bar, and the volume decreased by 1 ml under constant pressure of 100 bar. Calculate H
and E. [Given 1 bar = 105 N/m2] [JEE 2004]

3. H = 30 kJ mol–1 , S = 75 J / k / mol. Find boiling temperature at 1 atm. [JEE 2004]

(A) 400 K (B) 300 K (C) 150 K (D) 425 K
4. Spontaneous adsorption of a gas on a solid surface is exothermic process because [JEE 2004]

IA
(A) enthalpy of the system increases. (B) entropy increases.
(C) entropy decreases. (D) free energy change increases.
5. For the reaction : N2O4(g) 2NO2 (g)
(i) In a mixture of 5 mol NO2 and 5 mol N2O4 and pressure of 20 bar. Calculate the value of G for the reaction. Given

D
Gf° (NO2) = 50 kJ / mol, Gf° (N2O4) = 100 kJ / mol and T = 298 K.
(ii) Predict the direction in which the reaction will shift, in order to attain equilibrium
[Given at T = 298 K, 2.303 RT = 5.7 kJ / mol.] [JEE 2004]
6.

2 2
N
One mole of an ideal monoatomic gas at temperature T and volume 1L expands to 2L against a constant external
pressure of one atm under adiabatic conditions, then final temperature of gas will be :

T T
[JEE 2005]
SI
(A) T + (B) T – (C) 5 / 3 1 (D) 5 / 3 1
3  0.0821 3  0.0821 2 2
7. The ratio of P to V at any instant is constant and is equal to 1, for a monoatomic ideal gas under going a process.
What is the molar heat capacity of the gas. [JEE 2006]
O

3R 4R 5R
(A) (B) (C) (D) 0
2 2 2
O

8. The given reaction

2CO + O2  2CO2 H = – 560 kJ
2moles 1 mole
ET

is carried out in one litre container, if the pressure in the container gets changes from 70 atm to 40 atm as reaction
gets completed. Calculate U of the reaction. [1L atm = 0.1 kJ] [JEE 2006]
9. The direct conversion of A to B is difficult, hence it is carried out by the following shown path:

S(A  C) = 50 ; S(C  D) = 30; S(B  D) = + 20

The entropy change for the process A  B is [JEE 2006]

(A) 100 (B) – 60 (C) – 100 (D) + 60
10. The value of log10K for a reaction A B is :
(Given : rH298K = –54.07 kJ mol–1, r S 298K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1 ; 2.303 x 8.314 x 298 = 5705)
[JEE 2007]
(A) 5 (B) 10 (C) 95 (D) 100

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 THERMODYNAMICS
11. For the process H2O() (1 bar, 373 K)  H2O(g) (1 bar, 373 K), the correct set of thermodynamic parameters is :
[JEE 2007]
(A) G = 0, S = +ve (B) G = 0, S = –ve (C) G = +ve, S = 0 (D) G = –ve, S = +ve

12. Statement-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero.
Statement-2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction of decreasing
Gibbs energy. [JEE 2008]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True

13. Statement-1 : There is a natural asymmetry between converting work to heat and converting heat to work.
Statement-2 : No process is possible in which the sole result is the absorption of heat form a reservoir and its

IA
complete conversion into work. [JEE 2008]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True

D
14. Among the following, the state function(s) is(are) : [JEE 2009]
(A) Internal energy (B) Irreversible expansion work

15.
(C) Reversible expansion work

N
Among the following, the intensive property is (properties are) :
(D) Molar enthalpy

[JEE 2010]
SI
(A) molar conductivity (B) electromotive force
(C) resistance (D) heat capacity
16. One mole of an ideal gas is taken from a and b along two paths denoted by the solid and the dashed lines as shown
O
in the graph below. If the work done along the solid line path is ws and that along the dotted line path is wd, then the
integer closest to the ratio wd / ws is : [JEE 2010]
4.5
O

a
4.0

3.5

P 3.0
ET

(atm.)
2.5
2.0

1.5

1.0

0.5
b

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
V (lit.)

17. Match the transformation in column I with appropriate options in column II. [JEE 2011]
Column I Column II
(A) CO2(s)  CO2(g) (p) phase transition

(B) CaCO3(s)  CaO(s) + CO2(g) (q) allotropic change

(C) 2H   H2(g) (r) H is positive

(D) P(white, solid)  P(red, solid) (s) S is positive

(t) S is negative
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 THERMODYNAMICS
18. For an ideal gas, consider only P-V work in going from an initial state X to the final state Z. The final state Z can be
reached by either of the two paths shown in the figure. Which of the following choice(s) is (are) correct? [take S
as change in entropy and w as work done]. [JEE 2012]
(A) Sxz =Sxy + Syz

P(atmosphere)
X Y
(B) wxz = wxy + wyz
(C) wxyz = wxy
(D) Sxyz =Sxy Z

V (litre)

19. The reversible expansion of an ideal gas under adiabatic and isothermal conditions is shown in the figure. Which of
the following statement(s) is (are) correct ? [JEE 2012]
(P1, V1, T1)
(A) T1 = T2
(B) T3 > T1 isothermal
(C) wisothermal > wadiabatic P
(D) Uisothermal > Uadiabati (P2, V2, T2)
adiabatic

IA
(P3, V2, T3)
20. For the process [JEE 2015]
H2O ()  H2O (g) V
at T = 100°C and 1 atmosphere pressure, the correct choice is :
(A) Ssystem > 0 and Ssurroundings > 0 (B) Ssystem > 0 and Ssurroundings < 0

D
(C) Ssystem < 0 and Ssurroundings > 0 (D) Ssystem < 0 and Ssurroundings < 0

21. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally from 1.0 L to 2.0 L
against a constant pressure of 3.0 atm. In this process, the change inentropy of surroundings (ssur) in J K–1 is

22.
(1 L atm = 101.3 J)
(A) 5.763 (B) 1.013
N (C) –1.013 (D) –5.763
[JEE 2016]

An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) under different conditions. The correct statement(s) among
SI
the following is(are)
(A) the work done by the gas is less when it is expanded reversibly from V1 to V2 under adiabatic conditions as
compared to tht when expanded reversibly from V1 to V2 under isothermal conditions.
(B) The change in internal energy of the gas is (i) zero, if it is expanded reversibly with T1 = T2, and (ii) positive, if
O
it is expanded reversibly under adiabatic conditions with T1T2
(C) If the expansion is carried out freely, it is simultaneously both isothermal as well as adiabatic
(D) The work done on the gas is maximum when it is compressed irreversibly from (p2, V2) to (p1, V1) against
constant pressure p1 [JEE 2017]
O

23. The standard state Gibbs free energies of formation of C(graphite) and C(diamond) at
T = 298 K are
ET

fG°[C(graphite)] = 0 kJ mol–1
f G°[C(diamond)] = 2.9 kJ mol–1.
The standard state means that the pressure should be 1 bar, and substance should be pure at a given temperature.
The conversion of graphite [C(graphite)] to diamond [C(diamond)] reduces it volume by 2 × 10–6 m3 mol–1. If
C(graphite) is converted to C(diamond) isothermally at T = 298 K, the pressure at which C(graphite) is in equilibrium
with C(dimaond), is [Useful information : 1 J = kg m2s–2 ; 1 Pa = 1 kg m–1 s–2 ; 1 bar = 105 Pa] [JEE 2017]
(A) 29001 bar (B) 58001 bar (C) 14501 bar (D) 1450 bar
24. For a reaction taking place in a container in equilibrium with its surroundings, the effect of temperature on its
equilibrium constant K in terms of change in entropy is described by [JEE 2017]
(A) With increase in temperature, the value of K for endothermic reaction increases because unfavourable change
in entropy of the surroundings decreases
(B) With increase in temperature, the value of K for exothermic reaction decreases because favourable change in
entropy of the surroundings decreases
(C) With increase in temperature, the value of K for exothermic reaction decreases because the entropy changeof
the system is positive
(D) With increase in temperature, the value of K for endothermic reaction increases because the entropy change of
the system is negative
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 THERMODYNAMICS
25. A reversible cyclic for an ideal gas is shown below. Here, P, V, and T, are pressure, volume and temperature,
respectively. The thermodynamic parameters q, w, H and U are heat, work, enthalpy and internal energy, respectively.
[JEE(ADVANCED) 2018]

A(P1, V1,T1) C(P2, V1,T2)

Volume (V)

IA
B(P2, V2,T1)

Temperature (T)
The correct option (s) is (are)

D
(A) qAC = UBC and WAB = P2 (V2–V1) (B) WBC = P2 (V2–V1) and qBC = UAC
(C) CA < UCA and qAC = UBC (D) qBC =  HAC and CA > UCA

26.
N
 P , the plots of [A] and [P] with time at temperature T and T are given below.
For a reaction, A  1 2

[JEE(ADVANCED) 2018]
SI
10 10
[P]/(mol L 1)
[A]/(mol L 1 )

T1
O
T2
5 5
T2
T1
O

Time Time
If T2 > T1, the correct statement(s) is (are)
ET

T2
(Assume H0 and S0 are independent of temperature and ratio of lnK at T1 to lnK at T2 is greater than T1 . Here
H, S, G and K are enthalpy, entropy. Gibbs energy and equilibrium constant, respectively.)
(A) H0 < 0, S0 < 0 (B) G0 < 0, H0 > 0 (C) G0 < 0, S0 < 0 (D) G0 < 0, S0 > 0

27. Choose the reaction(s) from the following options, for which the standard enthalpy of reaction is equal to the
standard enthalpy of formation. [JEE(ADVANCED) 2019]
3 1
(A) O 2 (g)  O 3 (g) (B) S8 (s)  O 2 (g)  SO 2 (g)
2 8
(C) 2H2(g) + O2(g)  2H2O(l) (D) 2C (g) + 3H2(g)  C2H6(g)

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 THERMODYNAMICS
ANSWER KEY
EXERCISE -1

1. C 2. D 3. B 4. C 5. C 6. B 7. A
8. D. 9. D 10. B 11. A 12. A 13. D 14. A
15. C 16. D 17. A 18. C 19. D 20. D 21. C
22. A 23. B 24. C 25. D 26. C 27. B 28. C
29. C 30. A 31. B 32. C 33. B 34. D 35. D
36. B 37. B 38. D 39. D 40. D 41. A 42. A
43. C 44. C 45. D 46. A 47. C 48. B 49. A
50. B 51. B 52. A 53. A 54. C 55. D 56. D

IA
57. A 58. B 59. AC 60. C
61. –84.41 JK–1 mol–1 62. 0312 63. 5 64. +124.025 J
–1
65.  Sº = –33.6 JK 66. w = +3262.88 cal

D
67. At 298 K G° = + 432.274 KJ/mole, non spontaneous; T > 2484.8 K
68. P2 = 2.876 atm
69. (a) positive (b) negative (c) small, the sign of S is impossible to predict

70.
(d) negative (e) negative
G = – 5700 J/mol 71.
(f) negative
– 60.5 72.N 20 kJ / mol
SI
73. 28.72 kJ 74. – 6.12 J/K 75. 354

EXERCISE - 2 :
PART # I
O

1. A 2. C 3. A 4. D 5. A 6. C 7. B
8. B 9. C 10. B 11. A 12. C 13. C 14. A
O

15. C 16. C 17. D 18. C 19. B 20. C 21. C

22. D 23. C 28. D 29. A 30. C 31. D 32. A
ET

33. C
PART # II
1. A 2. H = 0 J, E = 10 J 3. A 4. C
5. (i) G = – 5700 J/mol (ii) backward shifting 6. B 7. B 8. H = U + (PV)
So, U = H – (PV) = – 560 – [40 – 70] (L atm) = (– 560 + 30 × 0.1) kJ = – 557 kJ.
9. D 10. B 11. A 12. D 13. A 14. A,D
15. A,B 16. 2 17. (A – p, r, s) ; (B – r, s) ; (C – t) ; (D – p, q, t)
18. A,C 19. A, D 20. B 21. C 22. A, C, D 23. C
24. A, B, C 25. B, C 26. A, C 27. A, B

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